US3799945A - 2-(n-2-cyanoethyldithiocarbamylmethylene)-5-hydroxy-4h-pyran-4-one and metal chelates - Google Patents

2-(n-2-cyanoethyldithiocarbamylmethylene)-5-hydroxy-4h-pyran-4-one and metal chelates Download PDF

Info

Publication number
US3799945A
US3799945A US00228368A US22836872A US3799945A US 3799945 A US3799945 A US 3799945A US 00228368 A US00228368 A US 00228368A US 22836872 A US22836872 A US 22836872A US 3799945 A US3799945 A US 3799945A
Authority
US
United States
Prior art keywords
pyran
hydroxy
cyanoethyldithiocarbamylmethylene
metal
chelates
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00228368A
Inventor
Amico J D
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Monsanto Co
Original Assignee
Monsanto Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Monsanto Co filed Critical Monsanto Co
Priority to US00228368A priority Critical patent/US3799945A/en
Application granted granted Critical
Publication of US3799945A publication Critical patent/US3799945A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/34—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D309/36—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
    • C07D309/40—Oxygen atoms attached in positions 3 and 4, e.g. maltol

Definitions

  • This invention relates to cyanoethyldithiocarbamic acid derivatives of kojic acid which are toxic toward microorganisms and are particularly valuable for controlling Venturia inaequalis, the pathogen responsible for apple scab disease.
  • Chloroalkenyl esters of cyanoethyldithiocarbamic acid have been described by DAmico as useful agents for the control of fungi, U.S. 3,284,287.
  • tApplicant herein combines the cyanoethyldithiocarbarnyl moiety with the kojic acid moiety to form new compounds which exhibit excellent fungicidal activity.
  • the subject compound is prepared by reaction of the ammonium salt of 2-cyanoethyldithiocarbamic acid and Z-(chloromethyl)-5-hydroxy-4H-pyran-4-one.
  • the chemical formula for the compound is I OH N C CHgCHzNH C (S) SClhio
  • the metal chelates are prepared by complexing a metal salt with the 2-(N 2 cyanoethyldithiocarbamylmethylene)-5-hydroxy-4H-pyran 4 one.
  • suitable metals from which chelates may be prepared are chromium, manganese, iron, cobalt, nickel, copper, zinc, cadmium, lead and mercury with the metals of atomic numbers of 26-30 being preferred.
  • the chelates are recovered as hydrates with the following postulated structure CHIS (S) CNHCHzCHa (IN-(H2O):
  • M is a metal ion and x is variable but generally is between 2-6 with x being about four when the chelates are dried at 45 C. overnight.
  • the new toxicants are effective bactericides and fungicides and may be applied to the habitat of the pathogen to prevent its growth and spread.
  • the bactericidal or fungicidal compositions containing the toxicant are applied to the area to be protected. If the area is already infected, the toxicant kills or inhibits further growth of the pathogen. If the treated area is pathogen-free, the toxicant keeps the area sterile by inhibiting growth of 3 ,799,945 Patented Mar. 26, 1974 "ice any pathogen which may invade the area.
  • the term habitat is used in its ordinary dictionary sense meaning the place where the pathogen normally lives and grows. Typical habitats are warm, damp places, for example, locker-room floors or in the case of plant pathogens, the habitat is the foliage of the plant.
  • Fungicidal compositions are prepared by combining one of the above described toxicants with a liquid or solid carrier.
  • the chelates are insoluble in water and organic solvents and the 2-(N-2-cyanoethyldithiocarbamyldithiomethylene)- 5 -hydroxy 4H pyran 4 one is insoluble in water but is soluble in certain organic solvents, for example, acetone and dimethyl formamide.
  • Aqueous dispersions of the toxicants may be prepared to form concentrates which may be diluted with water to form a spray suitable for application to the area to be protected. It is recommended that a dispersing agent be used to facilitate the formation of a more stable emulsion.
  • the toxicants may also be blended with an inert solid diluent such as talc, diatomaceous earth, fullers earth, etc., to form dry compositions which are dispersed in an aqueous medium to form a liquid spray.
  • an inert solid diluent such as talc, diatomaceous earth, fullers earth, etc.
  • any of the convenitional formulation and application techniques are applicable with the subject toxicants and includes combinations with the many known Wetting agents and inert carriers and includes combinations with other functional biological agents such as herbicides and insecticides.
  • the concentration of toxicant used varies depending upon the particular pathogen which the treatment is intended to control. Amounts of one percent to one part per million are effective with dosages of about p.p.m. being generally used. Of course, it is understood that greater or lesser amounts may be used and that the invention applies to any concentration at which toxic effects or inhibition of the bacteria or fungi is obtained.
  • the precipitate is recovered by filtration, washed with water until neutral to litmus and air dried at 2530 C.
  • 2-(N-2-cyanoethyldithiocarbamylmethylene)-5 hydroxy- 4H-pyran-4-one is recovered in 89% yield.
  • Example 2 The zinc chelate is prepared by adding at room temperature 4.5 g. (0.031 mole) of zinc chloride in 200 ml. of water to a solution containing 16 g.
  • a 1.0% stock solution or emulsion of the test material is prepared in a nontoxic solvent and diluted in agar to provide samples containing various concentrations of the test material.
  • Petri dishes are respectively filled with the test mixture and the plates thus prepared inoculated with the test organism. After a suitable incubation period, the plates are inspected and the concentration is recorded at which complete inhibition of the growth of the organism is obtained. Identical agar test plates with no test material present show normal uninhibited growth.
  • 2-(N-2-cyanoethyldithiocarbamylrn'ethylene) 5 hydroxy 4H-pyran- 4-one is applied to foliage of apple seedlings. Plants are selected for uniformity, sprayed with the toxicant and placed on carts to dry. Twenty-four hours later a spore suspension of Venturia inaequalis conidia is made and adjusted to a concentration of approximately 2,500,000 spores per ml. of water. The spore suspension is sprayed uniformly over the foliage of the treated and untreated trees. Immediately thereafter the plants are placed into the incubation chamber (100% relative humidity). Seventy-two hours later the trees are removed and after a drying period are placed on greenhouse benches.
  • the test consists of counting the number of parasitized leaves on each plant (3 replicates per treatment), determining the average number of parasitized leaves per tree for a given treatment, and expressing the result as percent control.
  • the percent control for each treatment is found by dividing the average number of parasitized leaves per tree in the untreated specimens into the average number of parasitized leaves per tree in the treated specimens, multiplying this number by 100 and subtracting it from 100. Comparisons are made with the commerical fungicide N-trichloromethylthio tetrahydropthalimide (Captan). The percent control based on untreated trees (average of three) at various concentrations is shown in the following table.
  • 2-(N-2-cyanoethyldithiocarbamylmethylene) 5 hydroxy-4H-pyran- 4-one is applied to foliage of tomato plants.
  • the procedure is essentially the same as described above for the apple tree tests except the treated and untreated plants are sprayed with a suspension of Phytophthora infestans the pathogen which causes the disease commonly called late blight.
  • Comparisons are made with the commercial fungicide manganese ethylenebis dithiocarbamate (Maneb). The percent control based on untreated tomato plants at various concentrations is shown in the following table.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

2 - (N - 2 - CYANOETYLDITHLIOCARBAMYLMETHYLENE) - 5 HYDROXY-4H-PYRAN-4-ONE AND METAL CHELATES THEREOF ARE EFFECTIVE AGENTS FOR CONTROLLING UNDESIRABLE MICROORGANISMS.

Description

United States Patent O 3,799,945 2-(N-2-CYANOETHYLDITHIOCARBAMYLMETHYL- ENE)-5-HYDROXY 4H PYRAN 4-0NE AND METAL CHELATES John Joseph DAmico, Akron, Ohio, assignor to Monsanto Company, St. Louis, M0. N Drawing. Filed Feb. 22, 1972, Ser. No. 228,368 Int. Cl. C07d 7/16 US. Cl. 260345.9 8 Claims ABSTRACT OF THE DISCLOSURE 2 (N 2 cyano'ethyldithiocarbamylmethylene) hydr0xy-4H-pyran-4-one and metal chelates thereof are effective agents for controlling undesirable microorganisms.
This invention relates to cyanoethyldithiocarbamic acid derivatives of kojic acid which are toxic toward microorganisms and are particularly valuable for controlling Venturia inaequalis, the pathogen responsible for apple scab disease. Chloroalkenyl esters of cyanoethyldithiocarbamic acid have been described by DAmico as useful agents for the control of fungi, U.S. 3,284,287. tApplicant herein combines the cyanoethyldithiocarbarnyl moiety with the kojic acid moiety to form new compounds which exhibit excellent fungicidal activity.
SUMMARY OF THE INVENTION 2 (N 2 cyanoethyldithiocarbamylmethylene) 5- hydroxy-4H-pyran-4-one and its metal chelates are potent agents for the control of fungi and bacteria. The new toxicants are valuable for controlling organisms on living plants because they exhibit fungicidal and bactericidal properties at low concentrations but are devoid of phytotoxic properties even at higher concentrations.
The subject compound is prepared by reaction of the ammonium salt of 2-cyanoethyldithiocarbamic acid and Z-(chloromethyl)-5-hydroxy-4H-pyran-4-one. The chemical formula for the compound is I OH N C CHgCHzNH C (S) SClhio The metal chelates are prepared by complexing a metal salt with the 2-(N 2 cyanoethyldithiocarbamylmethylene)-5-hydroxy-4H-pyran 4 one. Examples of suitable metals from which chelates may be prepared are chromium, manganese, iron, cobalt, nickel, copper, zinc, cadmium, lead and mercury with the metals of atomic numbers of 26-30 being preferred. The chelates are recovered as hydrates with the following postulated structure CHIS (S) CNHCHzCHa (IN-(H2O):
in which M is a metal ion and x is variable but generally is between 2-6 with x being about four when the chelates are dried at 45 C. overnight.
The new toxicants are effective bactericides and fungicides and may be applied to the habitat of the pathogen to prevent its growth and spread. The bactericidal or fungicidal compositions containing the toxicant are applied to the area to be protected. If the area is already infected, the toxicant kills or inhibits further growth of the pathogen. If the treated area is pathogen-free, the toxicant keeps the area sterile by inhibiting growth of 3 ,799,945 Patented Mar. 26, 1974 "ice any pathogen which may invade the area. The term habitat is used in its ordinary dictionary sense meaning the place where the pathogen normally lives and grows. Typical habitats are warm, damp places, for example, locker-room floors or in the case of plant pathogens, the habitat is the foliage of the plant.
Fungicidal compositions are prepared by combining one of the above described toxicants with a liquid or solid carrier. The chelates are insoluble in water and organic solvents and the 2-(N-2-cyanoethyldithiocarbamyldithiomethylene)- 5 -hydroxy 4H pyran 4 one is insoluble in water but is soluble in certain organic solvents, for example, acetone and dimethyl formamide. Aqueous dispersions of the toxicants may be prepared to form concentrates which may be diluted with water to form a spray suitable for application to the area to be protected. It is recommended that a dispersing agent be used to facilitate the formation of a more stable emulsion. The toxicants may also be blended with an inert solid diluent such as talc, diatomaceous earth, fullers earth, etc., to form dry compositions which are dispersed in an aqueous medium to form a liquid spray. In general, any of the convenitional formulation and application techniques are applicable with the subject toxicants and includes combinations with the many known Wetting agents and inert carriers and includes combinations with other functional biological agents such as herbicides and insecticides.
The concentration of toxicant used varies depending upon the particular pathogen which the treatment is intended to control. Amounts of one percent to one part per million are effective with dosages of about p.p.m. being generally used. Of course, it is understood that greater or lesser amounts may be used and that the invention applies to any concentration at which toxic effects or inhibition of the bacteria or fungi is obtained.
DESCRIPTION OF THE PREFERRED EMBODIMENTS Example 1 To a solution of 21 g. (0.3 mole) of 2-cyanoethylamine and 18.9 g. (0.3 mole) of concentrated ammonium hydroxide in 300 ml. of ethanol, there is added dropwise at 5-10 C., 22.8 g. (0.3 mole) of carbon disulfide. After stirring the mixture for one hour at 25-30 C., 48.2 g. (0.3 mole) of chloromethyl kojic acid is added in one portion. Upon the addition, the temperature rises to 58 C. and precipitate forms. After stirring the mixture at room temperature for 24 hours, 750 ml. of water is added and the mixture stirred for an additional half hour. The precipitate is recovered by filtration, washed with water until neutral to litmus and air dried at 2530 C. 2-(N-2-cyanoethyldithiocarbamylmethylene)-5 hydroxy- 4H-pyran-4-one is recovered in 89% yield. The product recrystallized from acetone melts at -166 C. Analysis gives 10.42% N and 24.19% S compared to 10.36% N and 23.72% S calculated for C H N O S Example 2 The zinc chelate is prepared by adding at room temperature 4.5 g. (0.031 mole) of zinc chloride in 200 ml. of water to a solution containing 16 g. (0.0619 mole) of 2-(N-2-cyanoethyldithiocarbamylmethylene)-5 hydroxy- 4H-pyran-4-one and 10.9 g. (0.0619 mole) of 25% sodium hydroxide in 400 ml. of water. After stirring two hours, the precipitate is recovered by filtration, Washed with water until neutral and air dried at 45 C. The zinc chelate of 2-(N-2 cyanoethyldithiocarbamylmethylene)- 5-hydroxy-4H-pyran-4-one is recovered in 100% yield (18 g.). Analysis gives low values for nitrogen probably because of interference of the metal ion and 19.56% S compared to 18.85% S calculated for By the procedure of Example 2, copper sulfate, nickel chloride, and cadmium sulfate are reacted to give the respective metal chelates. Analyses give 19.35% S compared to S calculated for c2QH1BN406S4Cu'4I I20; 18.61% S compared to 19.03% S calculated for and 18.15% S compared to 17.63% S calculated for C2oH1 N4O S4Cd 41 1 0.
To illustrate control of bacteria and fungi, a 1.0% stock solution or emulsion of the test material is prepared in a nontoxic solvent and diluted in agar to provide samples containing various concentrations of the test material. Petri dishes are respectively filled with the test mixture and the plates thus prepared inoculated with the test organism. After a suitable incubation period, the plates are inspected and the concentration is recorded at which complete inhibition of the growth of the organism is obtained. Identical agar test plates with no test material present show normal uninhibited growth.
At test concentrations of 100 ppm. ($5 2-(N-2- cyanoethyldithiocarbamylmethylene) hydroxy 4H- pyran-4-one and the Zn, Cu, Ni and Cd chelates thereof completely inhibit the growth of S. aureus, S. typhosa, Ps. aeruginosa, and A. niger.
In one embodiment of the invention 2-(N-2-cyanoethyldithiocarbamylrn'ethylene) 5 hydroxy 4H-pyran- 4-one is applied to foliage of apple seedlings. Plants are selected for uniformity, sprayed with the toxicant and placed on carts to dry. Twenty-four hours later a spore suspension of Venturia inaequalis conidia is made and adjusted to a concentration of approximately 2,500,000 spores per ml. of water. The spore suspension is sprayed uniformly over the foliage of the treated and untreated trees. Immediately thereafter the plants are placed into the incubation chamber (100% relative humidity). Seventy-two hours later the trees are removed and after a drying period are placed on greenhouse benches. Two weeks later apple scab tests are evaluated. The test consists of counting the number of parasitized leaves on each plant (3 replicates per treatment), determining the average number of parasitized leaves per tree for a given treatment, and expressing the result as percent control. The percent control for each treatment is found by dividing the average number of parasitized leaves per tree in the untreated specimens into the average number of parasitized leaves per tree in the treated specimens, multiplying this number by 100 and subtracting it from 100. Comparisons are made with the commerical fungicide N-trichloromethylthio tetrahydropthalimide (Captan). The percent control based on untreated trees (average of three) at various concentrations is shown in the following table.
The data show the toxicant of this invention is highly effective for controlling apple scab disease. No herbicidal effect upon the apple trees is observed even at the highest test concentration. In regard to phytotoxicity, at rates of 10 pounds per acre the toxicants of the examples exhibit essentially no phytotoxic properties against a spectra of broadand narrow-leafed plants.
In another embodiment of the invention, 2-(N-2-cyanoethyldithiocarbamylmethylene) 5 hydroxy-4H-pyran- 4-one is applied to foliage of tomato plants. The procedure is essentially the same as described above for the apple tree tests except the treated and untreated plants are sprayed with a suspension of Phytophthora infestans the pathogen which causes the disease commonly called late blight. Comparisons are made with the commercial fungicide manganese ethylenebis dithiocarbamate (Maneb). The percent control based on untreated tomato plants at various concentrations is shown in the following table.
Percent Control of Late Blight The data show that the toxicant of this invention is more effective at low concentrations than the commercial fungicide. No phytotoxic effects due to the toxicant is observed. Similar tests with the chelates of this invention give substantially the same degree of control of apple scab and late blight.
Although the invention has been illustrated by typical examples, it is not limited thereto. Changes and modifications of the examples of the invention herein chosen for purposes of disclosure can be made which do not constitute departure from the spirit and scope of the invention.
The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. 2 (N 2 cyanoethyldithiocarbamylmethylene)- 5-hydroxy-4H-pyran-4-one and metal chelates thereof.
2. The compound of claim 1, 2-(N-2-cyanoethyldithiocarbamylmethylene) -5 -hydroxy-4H-pyran-4-one.
3. The metal chelate of claim 1 in which the metal is selected from the group consisting of chromium, manganese, iron, cobalt, nickel, copper, zinc, cadmium, lead and mercury.
4. The metal chelate of claim 3 in which the metal has an atomic number of 26 to 30.
5. The metal chelate of claim 3 in which the metal is 6. The metal chelate of claim 3 in which the metal is copper.
7. The metal chelate of claim 3 in which the metal is nickel.
8. The metal chelate of claim 3 in which the metal is cadmium.
No references cited.
NORMA S. MILESTONE, Primary Examiner US. Cl. X.R. 424245, 283
US00228368A 1972-02-22 1972-02-22 2-(n-2-cyanoethyldithiocarbamylmethylene)-5-hydroxy-4h-pyran-4-one and metal chelates Expired - Lifetime US3799945A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US00228368A US3799945A (en) 1972-02-22 1972-02-22 2-(n-2-cyanoethyldithiocarbamylmethylene)-5-hydroxy-4h-pyran-4-one and metal chelates

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US00228368A US3799945A (en) 1972-02-22 1972-02-22 2-(n-2-cyanoethyldithiocarbamylmethylene)-5-hydroxy-4h-pyran-4-one and metal chelates

Publications (1)

Publication Number Publication Date
US3799945A true US3799945A (en) 1974-03-26

Family

ID=22856900

Family Applications (1)

Application Number Title Priority Date Filing Date
US00228368A Expired - Lifetime US3799945A (en) 1972-02-22 1972-02-22 2-(n-2-cyanoethyldithiocarbamylmethylene)-5-hydroxy-4h-pyran-4-one and metal chelates

Country Status (1)

Country Link
US (1) US3799945A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4055655A (en) * 1975-07-21 1977-10-25 National Research Laboratories Complexes of heavy metal ions and polyfunctional organic ligands used as antimicrobial agents
US4604471A (en) * 1983-11-23 1986-08-05 Basf Aktiengesellschaft Furan-3-carbohydroxamates and their use
US5258376A (en) * 1989-11-22 1993-11-02 Bernstein Lawrence R Pharmaceutical compositions of gallium complexes of 3-hydroxy-4-pyrones
US5298525A (en) * 1992-11-23 1994-03-29 University Technologies International, Inc. Diabetes prevention and treatment
US5883088A (en) * 1989-11-22 1999-03-16 Bernstein; Lawrence Richard Solid dosage forms for the oral administration of gallium

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4055655A (en) * 1975-07-21 1977-10-25 National Research Laboratories Complexes of heavy metal ions and polyfunctional organic ligands used as antimicrobial agents
US4604471A (en) * 1983-11-23 1986-08-05 Basf Aktiengesellschaft Furan-3-carbohydroxamates and their use
US5258376A (en) * 1989-11-22 1993-11-02 Bernstein Lawrence R Pharmaceutical compositions of gallium complexes of 3-hydroxy-4-pyrones
US5883088A (en) * 1989-11-22 1999-03-16 Bernstein; Lawrence Richard Solid dosage forms for the oral administration of gallium
US5968922A (en) * 1989-11-22 1999-10-19 Bernstein; Lawrence Richard Gallium complexes of 3-hydroxy-4-pyrones to treat or prevent hypercalcemia
US5981518A (en) * 1989-11-22 1999-11-09 Bernstein; Lawrence Richard Gallium complexes of 3-hydroxy-4-pyrones to treat or prevent calcium homeostasis disorders
US5998397A (en) * 1989-11-22 1999-12-07 Bernstein; Lawrence Richard Gallium complexes of 3-Hydroxy-4-pyrones to treat or prevent bone disease
US6004951A (en) * 1989-11-22 1999-12-21 Bernstein; Lawrence Richard Administration of gallium complexes of 3-hydroxy-4-pyrones to provide physiologically active gallium levels in a mammalian individual
US6048851A (en) * 1989-11-22 2000-04-11 Bernstein; Lawrence Richard Solid pharmaceutical compositions for the oral administration of gallium
US6087354A (en) * 1989-11-22 2000-07-11 Bernstein; Lawrence Richard Gallium complexes of 3-hydroxy-4-pyrones to treat cancer
US5298525A (en) * 1992-11-23 1994-03-29 University Technologies International, Inc. Diabetes prevention and treatment
US5470873A (en) * 1992-11-23 1995-11-28 University Technologies International, Inc. Diabetes prevention and treatment using gamma-pyrones

Similar Documents

Publication Publication Date Title
EP0031705B1 (en) Substituted 3-isothiazolones, salts and metal salt complexes thereof, compositions containing them and their use for combating bacteria, algae and fungi
US4238405A (en) Fungicidal 1,2-dichlorocyanovinyl compounds
EP0248086A1 (en) Imidazole derivatives, bactericides containing them, and process for their preparation
DE1806123A1 (en) Bis (thioureido) benzenes and their metal salts
PL80290B1 (en)
US3799945A (en) 2-(n-2-cyanoethyldithiocarbamylmethylene)-5-hydroxy-4h-pyran-4-one and metal chelates
US3801575A (en) 3-hydroxyisothiazoles
US3852444A (en) Fungicidal and bactericidal 2-(n-2-cyanoethyldithiocarbamylmethylene-5-hydroxy-4h-pyran-4-one and metal chelates
US4496559A (en) 2-Selenopyridine-N-oxide derivatives and their use as fungicides and bactericides
US3265563A (en) Phenyl nu-alkyl thiolcarbamate microbiocide
US3277142A (en) Aryloxyethyl and arylthioethyl esters of thiocarbamic acids
US3776920A (en) 2-(n-2-cyanoethyldithiocarbamyl-methylene)benzimidazoles
US3284287A (en) Inhibiting growth of fungi and bacteria
US5045555A (en) N-alkylbenzenesulfonylcarbamoyl-5-chloroisothiazole derivatives and microbicides containing the same
US4203999A (en) Bis(dithiocarbamate) salts
US3541155A (en) Phenoxypentanediones
US2913323A (en) Herbicidal method and composition employing bis(2-methyl-5-ethylpyridine) copper (ii) chloride
US2827415A (en) Heterocyclic compounds
SU701515A3 (en) Fungicidic agent
US3536742A (en) Alkylenebisdithiocarbamate complex compounds
US4100281A (en) Mono-5-substituted-thio-3-chloro-4H-1,2,6-thiadiazin-4-one antifungal agents
US3793312A (en) 1,2-dicyano-3,5-dithio-4-sulfonylimido cyclopentenes
US4143138A (en) 3-chloro-5-(optionally substituted heterocycloxy)-4h-1,2,6-thiadiazin-4-one antifungal agents
US4243675A (en) (Bis)dithiocarbamate) salts
US3271244A (en) Method of controlling bacteria and fungi with phosphorimidic triamide salts